IChO 1975 · Theory problem 4

Dilution of formic acid and degree of ionisation

The pH value of a solution containing 3 % by mass of formic acid (\(\rho = 1.0049\ \mathrm{g\,cm^{-3}}\)) is equal to 1.97.

Problem:

4.1 How many times should the solution be diluted to attain a tenfold increase in the value of ionisation degree?

Relative atomic masses: \(A_{\mathrm r}(\ce{H}) = 1.01;\quad A_{\mathrm r}(\ce{C}) = 12.01;\quad A_{\mathrm r}(\ce{O}) = 16.\)

Official English text of the problem.

Answers

  • 4.1: The required dilution factor is \(117.6 \approx 118\): the final solution volume should be approximately 118 times the initial volume.

Solution

4.1

Formic acid O=CO reacts with water O to form hydronium [OH3+] and formate O=C[O-]:

\[ \ce{HCOOH + H2O <=> H3O+ + HCOO-}. \]

We use the usual approximation of concentrations for activities and neglect the autoionisation of water.

The molar mass of formic acid is

\[ M=2(1.01)+12.01+2(16) =46.03\ \mathrm{g\,mol^{-1}}. \]

One litre of the initial solution has mass

\[ m_{\text{solution}} =(1000\ \mathrm{cm^3})(1.0049\ \mathrm{g\,cm^{-3}}) =1004.9\ \mathrm g, \]

and therefore contains \(0.03(1004.9)=30.147\ \mathrm g\) of formic acid. Its analytical concentration is

\[ c_1=\frac{30.147\ \mathrm g} {(46.03\ \mathrm{g\,mol^{-1}})(1\ \mathrm L)} =0.654942\ \mathrm{mol\,L^{-1}}. \]

The initial hydronium concentration follows from the pH:

\[ [\ce{H3O+}]_1 =10^{-1.97}\ \mathrm{mol\,L^{-1}} =0.0107152\ \mathrm{mol\,L^{-1}}. \]

Consequently, the initial degree of ionisation is

\[ \alpha_1=\frac{[\ce{H3O+}]_1}{c_1} =\frac{0.0107152}{0.654942} =0.0163605. \]

The required final degree is thus

\[ \alpha_2=10\alpha_1=0.163605. \]

For an analytical acid concentration \(c\) and degree of ionisation \(\alpha\),

\[ [\ce{H3O+}]=[\ce{HCOO-}]=c\alpha, \qquad [\ce{HCOOH}]=c(1-\alpha). \]

Hence the concentration form of the acid dissociation constant is

\[ K_a=\frac{c\alpha^2}{1-\alpha}. \]

At constant temperature, this gives for the two solutions

\[ \frac{c_1\alpha_1^2}{1-\alpha_1} = \frac{c_2(10\alpha_1)^2}{1-10\alpha_1}. \]

Cancelling \(\alpha_1^2\) and rearranging explicitly,

\[ c_1(1-10\alpha_1)=100c_2(1-\alpha_1), \]

so

\[ \frac{c_1}{c_2} =100\frac{1-\alpha_1}{1-10\alpha_1}. \]

Dilution conserves the total amount of acid, so \(c_1V_1=c_2V_2\). Therefore,

\[ \boxed{ \frac{V_2}{V_1} =\frac{c_1}{c_2} =100\frac{1-0.0163605}{1-0.163605} =117.6047 \approx118 }. \]

The \(1-\alpha\) factors must be retained because the final ionisation degree is about \(16.4\%\); the small-ionisation approximation would give an inaccurate dilution factor of \(100\).

The solution was checked against the official solution.